Condensation products



Patented Nov. 1939 I v r Nl'lED STATES PATENT OFFICE GONDENSATION PRODUCTS Herman A. Bruson and Clinton W. MacMulien, Philadelphia, Pa., assi'gnors to Riihm & Haas Company, Philadelphia, Pa.

No Drawing. Application February 'z, 1938,

\ Serial No. 189,172 1 12 Claims. (Cl. 260-457) This invention relates to condensation products. are conveniently prepared by the processes disobtained by the interaction of aldehydes and sulclosed in the copending applications of Herman A, fonates of aromatic ethers having the general Bruson, Ser. No. 118,267 filed December 30, 1936; formula R-- )--A--X in which R is a sulfonated Ser. No. 120,180 filed January 12, 1937; Ser. No.

aromatic radical nuclearly attached to the oxygen 86,344 filed June 20, 1936; and in U. S. Patent 5 atom, A is a divalent aliphatic group containing N grantea November 3 t at least two carbon atoms between 0 and X,,and The condensation of the aldehyde and any of X is a hydroxy, alkoxy, aryloxy, ester, halogen, the above types of sulfonic acid derivative is prefsulfuric ester or sulfonic acid group. erably carried out in the presence of sulfuric 10 It relates further to the process for preparing acid. The relative proportions of aldehyde and 10 these products by condensing the sulfonated arosulfonic derivative may be varied over a considermatlc. ether with an aldehyde in an acid medium. able range. It is preferable to use one moi of In carrying out this process we prefer to use aldehyde for each two aromatic nuclei irrespecformaldehyde or substances which yield formaltive of whether the compound being treated con-.

dehyde such as hexamethylenetetramjne, paratains one or more such nuclei. Thus, if there is 15 formaldehyde, methylal, etc., but we may employ one benzene ring in the sulfonated aromatic ether, other aldehydes such as acetaldehyde, butyraldetwo mols of ether will be reacted with one mol of hyde, aldol, crotonaldehyde, octyl aldehyde, benzaldehyde. If the ether contains two such nuclei, aldehyde, etc., or mixtures of any two or more. then it may be reacted with either one-half moi Some typical sulfonated aromatic ethers of the or one moi of the aldehyde. In this condensaabove general formula which may be condensed tion part of the sulfonated aromatic ether may with the aldehydes enumerated above are the be replaced by an equivalent amount of another following! I aromatic compound capable of condensing with n thealdehyde such as a sulfonated aromatic hy- I drocarbon, a monoor poly-hydroxy aromatic 25 compound of the phenol class, a sulfonated halo- 0OHr-CHa-o-oHzoH= -X genated aromatic hydrocarbon or a second sulfonated aromatic ether of one of the types de- R O CHPCHFO 'CHPCHPo- CHr-CH'X scribed above. In this manner mixed condensa- CHwHoO hX mm products can be obtained all of which are 30 r Hz0H soluble in water. The final products may all be neutralized with bases, organic or inorganic, and

most of the salts thus formed are soluble in water. R"O" CH'CHOOC CH All of the compounds prepared according to the (n0'-on,cHr-ocmcH,): present invention are soluble in water and are 35 R() -CH,OH -SCH QH Q .Q H Q powerful peptizing and dispersing agents. They are useful for preparing dispersions. of dyes, pig- ROCH'CH SOPCHCHPO CHCH'X ments, sulfur, zinc oxide, etc.; for preparing emul- In the foregoing formulas R and X have th sions; as textile assistants in dyeing and mer- 40 values given above. R. may be a simple h cerizing operations; as wetting agents in alkaline 40 I zene ornaphthalene group or a more highly conmedia; as tanning agents; as moth-proofing densedring system such as anthracene, phenang s d as detergentsthrene, carbazole, etc... and may contain, in addi- The nt i st at d y the f l w s tion to one or more sulfonic acid groups, other 51-- examp but it 18 not hmiiied t0 the exact r, substitutents such as alkyl, aralkyl, cycloaliryl, terials and conditions of operation shown as it 45 aryl, hydroxy, alkoxy groups or halogen. Th may otherwise be practiced within the scope of compounds in which R is a benzene ring carrythe appended claims. ing an alkyl group having from 4 to 18 carbon 7 Exampre 1 atoms or a cycloaliphatic group having 10 or more carbon atoms form particularly effective capil- 125 g. of p-ter.octyl phenoxy ethanol was 50 lary-active materials when condensed with an stirred while 125 g. of 98% sulfuric acid was added al hy dropwise, allowing the temperature to rise to 60 The sulfonated aromatic ethers which are used C. The cherry red mixture was stirred one hour,

as starting materials for the present invention during which the temperature fell to 37, C.

may be prepared by any desired process. 'I'hey Paraformaidehyde (7.5 g.) was added in small 55 powder by evaporation of the solvent.

portions during one hour at about 30 C'., and the mixture stirred. one-half hour. 200 cc. of water was added while cooling below 30 C., and the solution neutralized with 238 cc. of 25% sodium hydroxide. The turbid solution was cooled at 5 C. overnight and filtered from 160 g. sodium sulfate crystals. The clear filtrate (548 g.) contained 35% solids. It was found to be a powerful wetting and penetrating agent for textile materials, and excellent for the dispersion of pigments and carbon particles.

The solution may be dried to a pale yellow It is equally effective for wetting and penetration and, moreover, may be incorporated into dry mixtures as a dispersing agent. Its active component is the formaldehyde condensation product of OaNa Example 2 v 55 g. of bornyl phenoxy ethanol,

C10H1'lC6H4OCH2CH2OI-I was stirred while 50 g. of 98% sulfuric acid was added slowly. Thetemperature rose from 24 to about 65 C. The cherry red mixture was stirred and heated on the water bath one hour at about 60 C. Paraformaldehyde (3 g.) was added in several portions over a period of one-half hour Example 3] 70 g. of dodecyl phenoxy ethanol,

C12H25C6H4OCH2CH2OH was stirred while 50 g. of 98% sulfuric acid was added at about 25 C. The temperature rose to about 60 C. The brown mixture was heated on the water bath and stirred for one hour at 60 C. 3 g. of paraformaldehyde was added in portions to the pink mixture during one hour at a temperature below "30 C., and the viscous red paste stirred an hour longer at room temperature. 100 cc. of water was added at about 20 to 35 C. and the pink solution neutralized at a temperature below 30 C. with 97 cc. of 25% sodium hydroxide solution. The turbid white solution was cooled to approximately 5 C., allowed to stand overnight at this temperature and filtered from 86 g. of gummy residue. The turbid yellow filtrate contained 34% solids. ,It has powerful dispersing properties for pigments. Its active ingredient is the formaldehyde condensation product of Ca al-"CsHr-O-CHa'CHzOSOaNu S O:Na

. Example 4 72.5 g. of hexadecyl phenoxy ethanol,

C16H33-C6H4OCH2CH2OH was melted and stirred while 50 g. of 98% sulfuricacld was added, the temperature rising from 40 to about-60 C. The clear, red oil was heated and stirred one hour at about 60 C. 3 g. of paraarrasae formaldehyde was added after cooling to 30 C. and the mixture stirred one hour. 80 cc. of water was added and the solution neutralized with 109 cc. of 25% sodium hydroxide solution whereupon a yellow paste formed.

. The active ingredient of this product, the formaldehyde condensation product of CuHu-CeHt-O-CHaCHQO SOsNa OaNa is an active dispersing and emulsifying agent.

In a similar manner, formaldehyde and sulfonated octadecylphenoxy-ethyl sulfuric acid ester gave a soapy product useful as a dispersing agent.

Example 5 g. of p-ter.octyl phenoxy ethanol CsHir-CeH4- O CH2CH2OH I was stirred while 125 g. of 98% sulfuric acid was added over a period of about half an hour during which time the temperature rose from about 30 to 60 C. The red-brown-mixture was stirred and heated 6 hours at about 55. to 65 to complete sulfonation. 7.5 g. of paraformaldehyde was added in small portions during one hour at about 25 to 30 C., and the deep red oil was stirred one hour longer. 500 cc. of water was addedand the mixture heated on the steam bath to hydrolyze the sulfate ester group to ahydroxyl group, but leaving the aromatic sulfonic acid groups intact.

A portion of the solution was neutralized with solid potassium hydroxide, cooled to about 5 C., allowed to stand overnight at this temperature, and filtered from a small amount of residue. The clear, red filtrate had excellent penetrating action, even in strong alkaline solution.

-The ammonium salt was prepared, as well as salts of amines such as methylamine, cyclohexyl- I amine, morpholine, and ethanolamine, all of CsH 0 CHICHQOH where M is potassium, ammonium, sodium, etc.

Example 6 125 g. of 98% sulfuric acid was added to 125 g. of p-ter.octyl phenoxy ethanol. The temperature rose from 30 to about 60 C. and the mixture was stirred and heated one hour at about 50 C. 51g. of p-ter.octylphenol was added to the cherry-red mixture and stirring continued for 1 hours more. 7.5 g. of paraformaldehyde was added in small portions during one hour, and the red mixture stirred one hour longer. Water was added to the red mixture below 35 C., and the solution neutralized with 232 cc. of 25% sodium hydroxide solution. The orange solution was cooled to 5 to 10 C., allowed to stand overnight, and filtered. The turbid brown filtrate, containing 31% solids, is a good dispersing agent.

Example 7 125 g. of 98% sulfuric acid was added to 125 g. of p-ter.octyl phenoxy ethanol, allowing the temperature to rise to about 60 C., and the red mixture was stirred one hour at this temperature. 12 g. of acetaldehyde was added, accompanied by a rise in temperature and deepening of color, and the mixture stirred one hour. 200 cc. of water was added, followed by 50 g. of solid caustic, and neutralization was completed with 87 cc. of sodium hydroxide solution. The neutral solution was cooled to 5 to 10 (1., allowed to stand overnight, and filtered. The 111- trate was a clear, red solution containing solids, which on drying yielded a brown solid having good dispersing and penetrating power when dissolved in water.

Example 8 125 g. of 98% sulfuric acid was added dropwise to 125 g. of p-ter.octyl phenoxy ethanol, accompanied by a temperature rise to about 60 0., and the deep red mixture stirred one hour. 32 g. of 2-ethyl hexylaldehyde was added and the brown mixture stirred one hour. 200 cc. of water was added, followed by g. of solid sodium hydroxide while cooling. Neutralization was completed with 89 cc. of 25% smiium hydroxide solution. The neutral solution was cooled, allowed to stand overnight, and filtered. The clear, amber filtrate, when dried in vacuo, yielded a bright yellow paste containing 96% solids. Aqueous solutions of this material have good emulsifying properties.

Example 9 23 g. of 98%suliuric acid was added to 42 g.

of p-ter.octyl phenoxy ethoxy ethane,

mmQ-ocmcmocmom A OsNa Example 10 g. of sulfuric acid was added to 156 g. of p-ter.octyl phenoxy ethoxy ethyl chloride,

CaHu-CcI-Is-OCzI-IrOCaHsCl and the mixture stirred 6 hours at 60 C. 7.5 g.

of paraformaldehyde was added over a period oi one hour and the mixture was'stirred and allowed to stand overnight. 200 cc. of water was added, followed by 40 g. of solid and 10 cc. of 25% sodium. hydroxide. The neutral solution was cooled to 5- 10 C., allowed to stand overnight, and filtered. The product was a turbid, brown solution, containing 51% solids. The active prin ciple was the formaldehyde condensation product of CaH1'i-CcI-Is(SOaNa)OCaH4OCaH4Ci Example 11 61 g. of chlorsulionic acid was added to 156 g. of p-ter.octyl phenoxy ethoxy ethyl chloride at 5 to 15 C., and the mixture stirred three hours. 7.5 g. of paraiormaldehyde was added and the mixture stirred three hours. The mixture was neutralized with 250 cc. of 10% sodium hydroxide solution and heated in an autoclave, together with 66 g. of sodium sulflte and 540 cc. oi water for six hours at to 0., to replace the chlorine atom by a sullonlc acid group (-SOaNal The product was evaporated to dryness and ground to a powder, the active ingredient of which was the formaldehyde condensation product of Example 12 20 g of 98% sulfuric acid was added to 29.4 g. of B-phenoxy-p'-sec.octyloxy-diethyl ether,

CsHsOCaHaOCzI-IsOCaHn and the mixture heated and stirred iive hours at about 60 to 70 C. The dark mixture was cooled to 25, paraformaldehyde (1.5 g.) added, and the mixture stirred and allowed to stand overnight. 40 cc. of water was added and the brown solution neutralized with 47 cc. of 25% sodium hydroxide, cooled to 5 to 10 C., allowed to stand overnight, and filtered. The clear, brown d1 trate contained 37% solids.

Example 13 20' g. of 98% sulfuric acid was added to 28.8 g. of Mp-naphthyl) -p'-butyl-diethyl ether,

CiOHlOCflHdOCflHiOCAHB I and the brown mixture stirred and heated live hours at about 60 C. Paraiormaldehyde (1.5 g.)

was aded after cooling to about 30 C., and the mixture stirred one-half hour and allowed to stand overnight. Water was added and the red solution neutralized with 45 cc. of 25% sodium hydroxide solution, cooled to 5 to 10C.. allowed to stand overnight, and filtered. The clear. brown filtrate contained 36% solids, in which the active ingredient was the formaldehyde condensation product of NaOaSC1oI-Is-OCsHsOC2H4OCaI-Io Example 14 r 20 g. 98% sulfuric acid was added to 29.2 g.

, of p-ter.octyl phenoxy ethyl acetate,

. CsHn-CsI-Ir-OCI-IrCI-IsOOHI-Is and the-red mixture stirred and heated five hours at 60 C. The mixture was cooled to 30 C. and 1.5 g. of paraiormaldehyde added. The mixture was stirred for an hour, 40 cc. of water added, and the mixture neutralized with all cc. of 25% sodium hydroxide solution. The solution was cooled to 5 to 10C., allowed to stand overnight and filtered. The clear, orange solution contained 88% solids.

Example 15 20 g. of 98% sulfuric acid was added to 29.5 g. of p-phenoxy-13'-(p-ter.octyl phenoxy)diethyl ether, CsH17CsHa-0CH4OC:H4OCOHS, and the resulting brown paste heated and stirred five hours at about 60 to 65 C. Paraformaldehyde (24 g.) was added and the viscous red massallowed to stand ovemight It was heated to 40 C. and stirred. 30 cc. of water was added and the solution neutralized with 35 cc. of 25% sodium hydroxide. It was cooled, allowed to stand overnight, and filtered, yielding a turbid, orange solution.

Example 16 30 g. oleum (23%) was added to 37 g. of symdi(ter.butyl phenoxy)di-ethyl ether,

C4H9CsH4OC2H4OCaH4OCeH4C4Ha and thered, viscous mass heated and stirred six hours at about 60 C. 1.5 g. of paraformaldehyde Example 17 37 g. of 23% oleum was added to 89.2 g. of p-ter.octyl phenoxy ethoxy ethoxy ethyl chloride, CaH1'zCcH4OC2H4OC2H4OC2H4C1, and the mixture heated six hours at approximately 60 C. 10.5 g. of aqueous 37% formaldehyde solution was added and the viscous mass stirred and allowed to stand overnight. 100 cc. of water was added and the solution neutralized by the addition of 20 g. of solid and 1'7 cc. of 25%aqueous sodium hydroxide. The neutral solution was cooled to 5 to C., allowed to stand overnight, and filtered. The turbid, orange filtrate, when dried, formed a yellow paste. The active ingredient was the formaldehyde condensation product of l S OzNB may be aded prior or concurrently with the aldearomatic ether having the general hyde so as to form joint condensation products. A desirable ratio of reactants when such additions are made is one molecular equivalent of urea or guanidine to two molecular equivalents each of formaldehyde and sulfonated aromatic ether.

We claim:

1. A process which comprises condensing in an acid medium an aldehyde and a sulfonate of an formula R-OA'X in which R is a sulfonated aromatic radical, A is a divalent aliphatic radical containing at least two carbon atoms between X and the oxygen atom, and X is a member of the group consisting of hydroxyl, alkoxy, aryloxy, ester, sulfuric ester and sulfonic acid radicals and halogen.

2. A process which comprises condensing in an acid medium an aldehyde and a sulfonate of an aromatic ether having the general formula ROAX in which Risa sulfonated aromatic radical containing as a nuclear substituent an alkyl radical having from 4 to- 18 carbon atoms inclusive, A is a divalent aliphatic radical containing at least two carbon atoms between X and the oxygen atom, and X is a member of the group consisting of hydroxyl, alkoxy, aryloxy, ester,

sulfuric ester and sulfonic acid radicals and halogen.

3...A process which comprises condensing in:

an acid medium formaldehyde and a sulfonate of an aromatic ether having the general formula R0A-X in which R is a sulfonated aromatic radical containing as a nuclear substituent an alkyl radical havingfrom 4 to 18 carbon atoms inclusive, A is adivalent aliphatic radical containing at least two carbon atoms between X and the oxygen atom, and X is a member of the group consisting of hydroxyl, alkoxy, aryloxy, ester, sulfuric ester and sulfonic acid radicals and halogen.

4. A'process which comprises condensing in an acidmedium an aldehyde and asulfonate of an aromatic ether having the general formula RO--AX in which R is a sulfonated benzene ring containing as a nuclear substituent an alkyl radical having from 4 to 18 carbon atoms inclusive, A is a divalent aliphatic radical containing at least two carbon atoms between X and the oxygen atom, and X is a member of the group consisting of hydroxyl, alkoxy, aryloxy, ester,

sulfuric ester and sulfonic acid radicals andv halogen.

5. A process which comprises condensing in an acid medium an aldehyde and a sulfonate of ah aromatic ether having the general formula ROAX in which R is a sulfonated benzene ring containing as a nuclear substituent an alkyl radical having from 4 to 18 carbonatoms inclusive, A is a--CHaCHa group, and X is a member of the group consisting of hydroxyl, alkoxy,

aryloxy, ester, sulfuric ester and sulfonic acid radicals and halogen.

6. A process which comprises condensing in an acid medium formaldehyde and a sulfonate of an aromatic ether having the general formula R;O-AX in which R is a sulfonated benzene ring containing as a nuclear substituent an allgyl radical having from i to 18 carbon atoms inclusive, A is a --CH2--CH2 group, and X is a member 'of thegroup consisting of hydroxyl, alkoxy, aryloxy, ester, sulfuric ester and sulfonic acid radicals andhalogen.

7.-The product obtained by condensing an aldehyde and a sulfonate of an aromatic ether having the general formula RO-A-'X in which R. is a sulfonated aromatic radical, A is a divalent aliphatic radical containingat least two carbon atoms between X and the oxygen atom, and X is a member of the group consisting of hydroxyl,

alkoxy, aryloxy, ester, sulfuric ester and sulfonic acid radicals and halogen.

8. The product obtained bycq'ndensing an aidehyde and a sulfonate of an aromatic ether having the general 'formulaR-OA-X in which R is a sulfonated aromatic radical containing as a nuclear substituent an alkyl radical having from 4 to 18 carbon atoms inclusive, A is a divalent aliphatic radical containing at least two carbon atoms between X and the oxygen atom, and X is a member of the group consisting of hydroxyl, alkoxy, aryloxy, ester, sulfuric ester and sulfonic acid radicals and halogen.

9. The product obtained by condensing an aldehyde and a sulfonate of an aromatic ether having the general formula R-O-A-X in which R is a sulfonated benzene ring containing as a nuclear substituent an alkyl radical having from 4 to 18 carbon atoms inclusive, A is a divalent aliphatic radical containing at least two carbon atoms between X and the oxygen atom, and X aim-sac 1 is a member of the group consisting of hydroxyl, alkoxy, aryloxy, ester, sulfuric ester and suli'onic acid radicals and halogen.

10. The product obtained by condensing an aldehyde and a sulfonate of an aromatic ether having the general formula R-O-A-X in which R is a sulfonated benzene ring containing as a nuclear substituent an alkyl radical having from 4 to 18 carbon atoms inclusive, A is a -CH:CH: group, and X is a member of the group consisting of hydroxyl, alkoxy, aryloxy, ester, sulfuric ester and -sulionic acid radicals and halogen. I

11. The product obtained by condensing tormg 5 aldehyde and a sultonate at an 'rrlitic ether having the general formula R+-O-A-'2 in which R is a sulionated benzene ring containing as a nuclear substituent an alkyl radical having trom 4 to 18 carbon atoms inclusive, 4 is a -CH:CH: group, and X is a member of the group consisting of hydroxyl, alkoxy, aryloxy, ester. sulfuric ester and sultonic acid radicals and halogen.

12. The product obtained by condensingmrmaldehyde and a sulfonated p-ter.octyl phenoxy ethyl sulfuric acid ester. Y 1

ERMAN A. BRUBON. CLINTON W. MAOMULLEN. 

